This invention relates to the cleansers such as shampoos, liquid soaps, shower gels and similar products that are able to achieve improved pearlescence as compared to previous products made with other agents. In one aspect of the invention, 2-in-1 products with conditioning agents such as silicones are made which not only have improved pearlescence, but also have good stability.
A variety of cleansers, especially conditioning cleansers such as shampoos (so called xe2x80x9c2-in-1xe2x80x9d products), liquid soaps and shower gels are available. Such products use silicones of various types in combination with some type of suspending agent of system. For example, U.S. Pat. No. 4,741,855 to Grote et al uses long chain esters of ethylene glycol, esters of long chain fatty acids, or long chain amine oxides as stabilizing agents. U.S. Pat. No. 6,165,454 to Patel et al, describes the use of selected acrylates such as Aculyn-33 as a suspending agent. U.S. Pat. No. 5,213,716 to Patel et al describes the use of long chain alcohols such as C20-C40 alcohols as stabilizers for silicone containing hair care compositions. Other patents as background include U.S. Pat. No. 5,348,736 to Patel et al; U.S. Pat. No. 5,051,250 to Patel et al; U.S. Pat. No. 5,106,613 to Hartnett et al; and U.S. Pat. No. 4,997,641 to Hartnett et all. Certain commercial products have tried using a combination of cetyl and stearyl alcohols for a stabilizing effect.
These previous attempts have resulted in some degree of success, but there still remains a need to obtain additional pearlizers, especially pearlizers which are capable of stabilizing compositions which contain silicones. In one particular embodiment, formulations are made which not only achieves good pearlescence, but also stabilizes cleansing compositions containing silicones at lower temperatures.
The invention comprises the use of behenyl alcohol, a straight chain alkyl with an average of 22 carbons, in cleansers, especially shampoos. In one particular type of cleansers, a conditioning agent is also present. In particular, compositions of this invention comprise:
(a) 4.00-30.00 weight % (for example, 7-20 weight %) of an anionic material selected from the group consisting of water soluble lipophilic sulfates and/or sulfonates of 8 to 22 carbon atoms, preferably of 10 to 16 or 10 to 18 carbon atoms, more preferably of 10 to 14 or 16 carbon atoms;
(b) 0.25-4.0 weight % (for example, 1-2 weight %) behenyl alcohol.
(c) 0-10.00 weight 5 (particularly 0.10-10.00 weight %) (for example, 0.5-4.0 weight %) of a non-ionic material selected from the group consisting of a higher fatty alkanolamide such as those having 8-22 carbons, for example, cocodiethanolamide, cocoethanolamide, cocoamidopropyl dimethylamine, coco amine, cocoamine oxide, and cocoaminopropionic acid;
(d) 0-10.00 weight % (for example, 0.05-10.00 weight % and more particularly 1-3 weight %) of an amphoteric material (sometimes referred to as a zwitterionic material) selected from the group consisting of derivatives of aliphatic quaternary ammonium, phosphonium or sulfonium compounds in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8-22 carbons and one contains an anionic water-solubilizing group (for example, a carboxyl, sulfonate, sulfate, phosphate or phosphonate) C8-C18 alkyl betaines and sulfobetaines, and C8-C18 alkyl amphoacetates and propionates;
(e) optionally a cationic material which is a cationic surface active fiber conditioning agent, which may be considered to be secondary conditioning agents in the invented fiber conditioning compositions, are selected from the group consisting of
(i) 0-5.0 weight % (for example, 0.05-5.0 weight % and more particularly 0.2-0.5 weight %) of one or more quaternary ammonium salts of formula: 
xe2x80x83wherein R9 is a lower alkyl having 1-4 carbons; R10 and R11 may be the same or different and are each selected from the group of higher alkyls having 10-40 carbons; R12 is selected from the groups defined for R9 and R10; Xxe2x88x92 is a salt forming anion selected from the group consisting of a halide (for example, chloride and bromide), lower (C1-C3) alkylsulfates (for example, methosulfate and ethosulfate), lower (C1-C3) carboxylic acid radicals (for example, acetate) and citrate; and
(ii) 0.0-2.0 weight % (for example, 0.05-0.4 weight %) of one or more water soluble cationic cellulosic polymers selected from the group consisting of hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, galactomannan gums;
(f) 0-5 weight % (for example, 0.25-5.0 weight % and more particularly 0.25-4 weight %) of a silicone selected from the group consisting of water insoluble organosilicone compounds selected from the group consisting of:
(i) dimethicones, dimethicone derivatives and mixtures of the foregoing having a viscosity in the range of 5-100,000 centipoise (cps), particularly 30-70,000 cps and even more particularly 60,000 cps; for example organosilicone compounds of 
xe2x80x83wherein R1, R2, R3, R5, R6, and R7 may be the same or different and are each independently selected from the group consisting of alkyls of 1-6 carbons (especially 1-2 carbons) and z is selected so that the viscosity described above is achieved; and
(ii) aminosilicones of Formula II 
xe2x80x83wherein R1, R2, R3, R5, R6, and R7 may be the same or different and are each independently selected from the group consisting of are alkyls of 1-6 carbons (especially 1-2 carbons); and R4 is R8xe2x80x94NHxe2x80x94CH2CH2xe2x80x94NH2, R8 is an alkylene of 3-6 carbons;
x=is an average value and is a number in the range of 500-10,000, particularly 500-4,000, more particularly 500-1000, and especially 750-800; and
y=is an average value and is a number in the range of 1-10, particularly less than 5 and especially 1.
(iii) mixtures of (i) and (ii), especially mixtures where high viscosity materials are mixed with lower viscosity materials (examples of suitable materials include a dimethicone from Dow Corning (Midland, Mich.) known as Dow Coming Fluid 200, and a dimethicone from Union Carbide (Tarrytown, N.Y. known as Silicone L-45);
(g) optionally, one or more members selected from the group consisting of an effective amount of a pH modifying agent; an effective amount of a viscosity modifying agent; an effective amount of a preservative; fragrance, a coloring agent; and
(h) the remainder water; provided that if silicone is used, a sufficient amount of behenyl alcohol or behenyl alcohol in combination with an additional suspending agent is used to stabilize the composition.
Note, that although other surface active compounds with fiber conditioning properties may also be employed, at least in part. Thus, imidazolinium salts and betaines, and such cationic and amphoteric materials as are described in U.S. Pat. No. 4,000,077 may be substituted for at least some of the quaternary ammonium salt, as may be complexes of cationic and anionic surfactants such as have been described in U.S. Pat. Nos. 4,786,422; 4,888,119; and 4,929,367, which are incorporated by reference herein as to the description of these materials.
For the anionic materials (also referred to herein as anionic surfactants or anionic detergents), examples include higher (C8-18) alkyl sulfates, higher paraffin sulfonates, higher olefin sulfonates, higher fatty acid monoglyceride sulfates, higher fatty alcohol lower alkoxy (and polyoxy) sulfates, linear higher alkyl benzene sulfonates, and dialkyl sulfosuccinates. The most preferred of these anionic detergents for the examples of shampoos described herein are the higher alkyl sulfates of 10 to 16 carbon atoms and the higher alkyl lower alkoxy sulfates of 10 to 18 carbon atoms (preferably with the higher alkyl thereof being lauryl and with 2 or 3 ethoxy groups per mole). However, such alkyls may be of 10 to 16 carbon atoms and the alkoxy content may be of 1 to 20 per mole, such as 2 to 6 ethoxy groups per mole. A most preferred higher fatty alcohol sulfate is lauryl sulfate and a particularly preferred higher fatty alcohol poly-lower alkoxy sulfate is di- or triethoxylated lauryl alcohol sulfate. Most preferably the anionic detergent will be a mixture of higher alkyl sulfate and higher alkyl ether sulfate, with either being present in greater or equal proportion, and with the ratio of amounts of such components being in the range of 10:1 to 1:10 or 7:1 to 1:7, for example, 1:5 to 5:1, when both such anionic detergents are present.
The anionic detergents will be employed in the forms of their water soluble salts, which will usually be salts of alkali metals (sodium, potassium), ammonium, amines (such as dimethylamine and trimethylamine) or lower alkanolamines (such as triethanolamine, diethanolamine and monoethanolamine). Exemplary of useful detergents are ammonium lauryl sulfate, sodium lauryl diethoxy sulfate, arumonium lauryl triethoxy sulfate, sodium alpha C16 olefin sulfonate, sodium C14 paraffin sulfonate, sodium coco monoglyceride sulfate, triethanolamine cetyl sulfate and dimethylamine myristyl sulfate. However, for best results it is preferred to utilize higher alkyl sulfate, higher alkyl poly-lower alkoxy sulfate or a mixture of such higher alkyl sulfate and such higher alkyl ether sulfate, such as lauryl sulfate and lauryl diethoxy sulfate or lauryl triethoxy sulfate, often with the higher alkyl sulfate being present in greater proportion and in ammonium, triethanolamine and/or sodium salt form. (See U.S. Pat. No. 5,415,857 assigned to Colgate-Palmolive Co.)
One particular group of anionic materials useful in this invention include 4-30 weight % (especially 5-20 weight %) of one or a mixture of ammonium lauryl sulfate and sodium laureth (with 2 moles ethylene oxide) sulfate.
Non-ionic materials useful in this invention include higher fatty alkanolamides which have long been known as foaming agents and foam stabilizers. Such compounds will usually have 8-22 carbon atoms in the compounds and have, for example, 12 to 16 carbon atoms in the acyl group, which is reacted with a lower (1 to 3 carbon atoms) mono- or dialkanolamine. In the present formulations the best alkanolamides are considered to be lauric monoethanolamide, cocodiethanolamnide and cocoethanolamide.
Amphoteric materials (also referred to herein as amphoteric surfactants or zwitterionic materials) can be exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, or sulfonium compounds in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8-18 carbons and one contains an anionic water-solubilizing group such as a carboxyl, sulfonate, sulfate, phosphate or phosphonate group. These can generally be represented by the following formula 
wherein Ra is a C1-3 alkyl or monohydroxy alkyl; Rb is a C8-18 alkyl, alkenyl or hydroxy alkyl radical with 0-10 ethylene oxide moieties and 0-1 glyceryl moiety; Rc is a C1-4 alkylene or hydroxyalkylene, x is 1 when Y is a sulfur atom and X is 2 when Y is a nitrogen or phosphorous atom, Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
One group of amphoteric includes
4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;
5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentae-1-sulfate;
3-[P,P-diethyl-P-3,6,9-trioxatetradexocylphosphonio]-2-hydroxypropane-1-phosphate;
3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio]-propane-1-phosphonate;
3-[N,N-dimethyl-N-hexadecylammonio]-propane-1-sulfonate;
4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)arnmonio]-butane-1-carbonate;
3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;
3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; and
5-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-32-hydroxypentane-1-sulfate.
Another group of amphoteric materials are the betaines such as high alkyl betaines including cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxy-ethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxy-ethyl)carboxy methyl betaine, stearyl bis-(2-hydroxy-propyl)-carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, etc. (See U.S. Pat. No. 4,741,855 assigned to the Procter and Gamble Co.)
Particular examples of amphoteric materials include cocoamidopropyl betaine, cocobetaine, cocosultaine, especially when one or more of non-ionic and zwitterionic materials can be used, and where the total of non-ionic and zwitterionic material are in the range of 5-10 weight %.
Generally amphoteric surfactants will be selected from the group consisting of C8-18 alkyl betaines and sulfobetaines, and C8-18 alkyl amphoacetates and propionates. Suitable betaines and sulfobetaines have the formula 
where R31=C8-C22 alkyl, R35 COxe2x80x94 (where R35=C8-C22), R36xe2x80x94C(O)xe2x80x94NH2xe2x80x94(CH2)3xe2x80x94 (where R36=C8-C22);
R32=C1-C4 alkyl;
R33=C1-C4 alkyl;
R34=C1-C4 alkyl;
and Xxe2x88x921=is selected from the group consisting of COOxe2x88x921; OSO3xe2x88x921; CH3CH2COOxe2x88x921 
Other amphoteric materials include compounds of formula 
where R37=cocoyl.
Typical betaines and amido alkyl betaines include decyl dimethyl betaine or 2-(N-decyl-N,N-dimethylammonio) acetate, cocodimethyl betaine or 2-(N-coco-N,N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, cocoamidopropyl dimethyl betaine and laurylmidoethyl dimethyl betaine. Typical sulfobetaines or sultaines similarly include cocodimethyl sulfobetaine, or 3-(N-coco-N,N-dimethylammonio) propane-1 sulfonate, myristyl dimethyl sulfobetaine, lauryl dimethyl sulfobetaine, cocoamidoethylsulfobetaine and cocamidopropylhydroxy sultaine.
Another group of suitable amphoteric surfactants are the C8-C18 alkyl amphoacetates and propionates corresponding to the following formula: 
wherein R8 C(O) is a C8-C18 acyl group, R9 is a methyl or ethyl group, and M is a salt forming group such as sodium or potassium. A substitute for the described amphoacetate or amphopropionate compound is sodium cocoamphohydroxypropyl sulfonate. Sodium cocoamphoacetate is a preferred material. (See U.S. Pat. No. 5,747,435).
When an amphoteric surfactant is used in the compositions of the invention (especially shampoos), the proportion of the amphoteric surfactant generally will be in the range of about 2.5% to about 21% by weight of the final composition. A particular proportion of amphoteric surfactant will be selected from the range of about 4% to about 13% by weight and, more particularly, from the range of about 6% to about 10% by weight of the final composition.
In a particular group of compositions, the proportion of the surfactant mixture (total of all surfactants used) will be from about 8% to 28% by weight of the composition; and in a more particular composition the proportion of the surfactant mixture will be from 13% to 22% by weight.
For the cationic material the preferred quaternary ammonium salts are of the formula 
[R9R10 R11 R12 N+][Xxe2x88x921], wherein at least one of the R groups is lower alkyl and at least one is higher alkyl, with the others being higher and/or lower alkyl. Preferably R9 is lower alkyl, such as of 1 to 4 carbon atoms, R10 and R11 are higher alkyls of 10 to 40 carbon atoms, R12 is such a higher alkyl or lower alkyl, and Xxe2x88x92 is a salt forming anion selected from the group consisting of halides (for example, chloride and bromide), lower (C1-C3 alkylsulfate (for example, methosulfate and ethosulfate), lower (C1-C3) carboxylic acid radicals (for example, acetate) and citrate. The lower alkyl will preferably be of 1 to 3 carbon atoms, more preferably being of 1 or 2 carbon atoms, and most preferably, in most cases, will be methyl, and the higher alkyl will preferably be of 10 to 22 carbon atoms, more preferably 12 to 18 or 20 carbon atoms, most preferably of 14 to 18 carbon atoms, for example, 16 or about 16 carbon atoms. The anion is preferably a alogen, such as chlorine, bromine or iodine, with chlorine and bromine being preferred and with chlorine being more preferred. The number of lower alkyls on the quaternary nitrogen will preferably be 1 or 2 and the number of higher alkyls will usually be 2 or 3. It has been found to be desirable to have at least 30 carbon atoms in the quaternary ammonium salt and preferably at least 34. The most preferred higher alkyl is cetyl, the most preferred lower alkyl is methyl, and the most preferred quaternary ammonium halide is tricetyl methyl ammonium chloride. Nevertheless, it is within the invention to employ other quaternary ammonium halides, such as distearyl dimethyl ammonium chloride, dilauryl dimethyl ammonium bromide, stearyl cetyl dimethyl ammonium chloride, trimyristyl ethyl ammonium bromide and trilauryl ethyl ammonium chloride, and other fiber and hair conditioning cationic surfactants as at least part of the fiber and/or hair conditioning cationic surfactant (surfactant is short for surface active agent) content of the present compositions.
Another category of cationic materials are natural polymers such as hydroxy alkyl celluloses and alkyl hydroxy alkyl celluloses. Cationic hydroxy alkyl celluloses and their preparation are described in British Patent Number, 1,166,062 assigned to Union Carbide and U.S. Pat. No. 5,747,435 assigned to Colgate-Palmolive Co. These hydroxy ethyl celluloses are marketed under the trade designation JR 125, JR 30M, and JR 400 and are believed to have a molecular weight in the range of 150,000-400,000 and a degree of substitution of a quaternary group of about 0.3. Alkyl hydroxy alkyl celluloses having the same formula as hydroxy alkyl cellulose, but with additional alkyl substituents at other sites on the anhydroglucose unit are also available. More particularly, the ethyl hydroxy ethyl celluloses are available under the tradename xe2x80x9cModocollxe2x80x9d with a molecular within the range of about 50,000-500,000 and a degree of substitution of about 0.1-0.8. Other suitable natural cationic polymers are the galactomannan gums, for example, guar gum and hydroxy alkylated guar gum. The molecular weight of guar gum is believed to be in the range of 100,000-1,000,000. A suitable cationic guar gum carrying the group xe2x80x94CH2CHxe2x95x90CHCH2N(CH3)Cxe2x80x94 with a degree of substitution of about 0.2-0.8 is commercially available under the tradenames Jaguar C-17 and C-13. The preferred cationic cellulose polymer is Polyquaternium-10 which is a polymeric quaternary ammonium salt of hydroxyethyl cellulose reacted with a trimethyl ammonium substituted epoxide. The proportion of the cationic natural polymer may be, for example, in he range of about 0.05-1.0%, particularly 0.1-0.8% and, more particularly, in the range of about 0.2-0.7% by weight of the final composition. When the cationic natural cellulose or galactomannan gum polymers are used, up to one-half of their weight many be substituted by a second non-cellulosic, cationic polymer that is soluble in the final composition. Examples of these include dialkyldiallyl ammonium salt (such as a halide) homopolymers or copolymers, for example, dimethyl ammonium chloride homopolymer, dimethyldiallyl ammonium chloride/acrylamide copolymer containing at least 60% dimethyldiallyl ammonium chloride monomer, dimethyldiallyl ammonium chloride/acrylic acid copolymer containing at least 90% dimethyldiallyl ammonium chloride monomer, vinyl imadazolevinyl pyrrolidone copolymers containing at least 50% vinyl imidazole and polyethyleneimine. Particular examples of cationic polymers include Merquat 100 (a polymer of diallyldimethyl ammonium chloride (charge density of 126)) and Luviquat 905 (a 95% vinyl imidazole/5% vinylpyrrolidone copolymer (charge density of 116)). Other examples include any of the xe2x80x9cPolyquaternium-Xxe2x80x9d compounds where X is a whole number.
Particular cationic materials useful in this invention include one or more member selected from the group consisting of Polyquatemium-6, Polyquaternium-7, Polyquatemium-10, Polyquatemium-16, Polyquatemium-80, cationic guar gum, and distearyl dimonium chloride, wherein the total amount of cationic materials used is in the range of 0.05-1 weight %, especially 0.05-0.5 weight %.
The cationic materials described for this invention are preferably in aqueous form and may be dissolved or dispersed in an aqueous medium such as water.
Silicones useful in this invention include dimetlucones, aminosilicones and dimethiconols, especially dimethicones having a viscosity in the range of 30,000-100,000 centistokes (xe2x80x9ccstxe2x80x9d), and particularly 60,000 cst. Example of such materials include the silicones listed in Tables A, C, E, G, I, K, M, O, Q, S, U, W, Y, AA, AC, AF, and AM.
One particular class of silicones is dispersed, insoluble, non-volatile silicone (especially polydimethylsiloxane). In one embodiment, 4-30 weight % of the anionic marterial; 0.1-10 weight % of a dispersed, insoluble, non-volatile silicone (especially polydimethylsiloxane) and sufficient behenyl alcohol to stabilize the silicone are used.
The target pH of the compositions of the invention is in the range of 5.5-6.8, especially in the range 6.0-6.5. Agents suitable for modifying pH include those known in the art, for example, sodium phosphate monobasic and citric acid to decrease pH, and sodium phosphate dibasic and sodium hydroxide to increase pH.
The target viscosity of the compositions of the invention is in the range of 2,000-8,000 centipoise (xe2x80x9ccpsxe2x80x9d). Viscosity modifiers known to those in the are may be used, particularly in the range of 0.1-2.0 weight % (more particularly 0.5 weight %). For example, viscosity may be increased by the addition of sodium chloride and viscosity may be decreased with the addition of sodium cumene sulfonate.
Preservative may be used in amounts in the range of 0.0-0.5%, particularly 0.0-0.1%. Examples include KATHON (for example, effective amounts up to 0.07%), formaldehyde (for example, 0.1-0.2%), hydentoin (for example, effective amounts up to 0.5%) or mixtures of the foregoing.
To make the invented compositions the various required components are dissolved and/or suspended in an aqueous medium. For shampoos, such medium may include various non-interfering normal shampoo composition constituents known in the art, which have been specifically mentioned herein because they are especially desirable components of the present compositions and contribute in a significant manner to its desirable properties.
Behenyl alcohol is used in this invention. This long chain alcohol is preferably a saturated compound, with the hydroxy group being terminally located. Behenyl alcohol will normally be of a distribution of C20-C24 homologous alcohols and typically all are of even numbers of carbon atoms, averaging 22 carbon atoms (on a weight basis). Behenyl alcohol has been found to be especially effective in this invention. (When the average number of carbon atoms in the chain is less than 18 the desired effectiveness of such alcohols in the present formulations is decreased, with the stabilization, fiber conditioning and pearlizing actions being diminished.). In addition to the mentioned long chain alcohols, related compounds such as corresponding alkoxylated alcohols, corresponding fatty acids and long chain saturated primary alcohol esters, may be substituted in a minor proportion (for example, less than 50% of the behenyl alcohol component). When such a substitution is made, ethoxylated alcohols are preferred as the alkoxylated alcohols and will normally contain up to 20 ethoxy groups per mole, such as 10 to 20, for example, about 13 or 15. Thus, the behenyl alcohol normally will be employed alone or in mixture with related compounds from the xe2x80x9cderivativesxe2x80x9d group, with the alcohol being the major proportion of the final xe2x80x9calcohol plus derivativesxe2x80x9d content. Examples of commercial materials which may be employed in the present compositions.
Behenyl C-22 alcohols (having an average of 22 carbon atoms in its chain as described above) may also be used in combination with other ingredients in sufficient amounts to stabilize the final product. Examples of such combinations include, for example, 0.25-4.0 weight % behenyl alcohol plus 0.1-2.0 weight % of an acrylic stabilizing agent selected from the group consisting of polyacrylic acid, derivatives of polyacrylic acid, acrylates copolymer and derivatives of acrylates copolymer such as those sold by Rohm and Haas (Philadelphia, Pa.) under the names Aculyn-22, -28 and -33.
The composition of this invention may be made by a variety of techniques. Such techniques are described in the Examples.
It should be noted that different levels of conditioning may be appropriate for different types of hair. Some types of hair such as bleached or processed hair require high level of conditioning. Other types of hair only need a small amount of conditioning. The compositions of this invention may be formulated to accommodate all types of conditioning requirements.
It should also be noted that while the term xe2x80x9cmaterialsxe2x80x9d has been used, it is to be understood that for anionic, nonionic and amphoteric components the term xe2x80x9csurfactantsxe2x80x9d or xe2x80x9cdetergentsxe2x80x9d could also be used.